Nitration of organic carbohydrates



Patented Jan. 11, 1938- UNITED STATES PATENT OFFICE NITRATION OF ORGANIC GARBOHYDRATES Joseph A. Wyler, Allentown, Pa, assignor to Trojan Powder Company, a corporation of New York No Drawing. Application October 12, 1935, Serial No. 44,687

6 Claims. (01. 260-145) My invention relates to improvements in the nitrated sugars is raised very considerably by the nitration of organic carbohydrates, and more pardissolved nitrated starch. Applicant hasv also ticularly relates to improvements in the simuldiscovered that if a sugar such as cane sugar, taneous nitration or co-nitration of a plurality of glucose or cerelose is mixed with 10% or more of 5 carbohydrate bodies. My invention relates speits Weight of powdered corn starch or cassava cifically to the co-nitration or simultaneous nistarch for example and .this mixture is nitrated tration of sugar and of carbohydrates such as by the action of nitric acid, preferably in adstarch. One of the objects of my invention is to mixture with a dehydrating agent such as sulprovide means for the preparation of explosive furic or phosphoric acids in the same manner that in bodies having improved characteristics and castarch is nitrated, a plastic mass results in the ]Q pable of being used to advantage as explosives and nitrator, which mass can rea ly be Separated in the formulation of explosive mixtures, to give from the spent acid and transferred to a kneadproperties in the finished explosive which are not ing trough supplied with a steadily flowing stream obtainable from the simple nitrated car bohyof tap water, and here readily caused to lose its drates or even from a mixture of these nitrated doughiness and to revert to a fine powder which 15 carbohydrates. This application is a continuacan be handled as a powder at ordinary temtion in part of my pending application S. N. peratures or higher. Thus I am able to stabilize 727,592, filed May 25, 1934. the nitrated sugar mixture very readily at ordi- The nitration of various sugars such as cane nary temperatures and also to dry same at a sugar, glucose, levulose, etc. and of mixtures of temperature of approximately 40 C. 20

sugars with glycerine, glycol and certain of their .As descriptive of a method that I may use in derivatives is well known and is described in the the nitration of a starch-sugar mixture, I give general literature as well as disclosed in domestic the following example:

and foreign patents. 100 lbs. of finely ground cane sugar is thor- The chief reasons for the use of sugar nitrates oughly mixed with 25 lbs. of dried corn starch and have been cheapness of product and lowering of the mixture fed to 360 lbs. of 95% HNOs, keepfreezing point of nitroglycerine and, so far as ing the nitration mixture at a low temperature, applicant knows, only nitrated cane sugar has say, below 20 C. At the end of this operation all actually been utilized in commercial explosives, of thestarch and all of the sugar will have gone and when thus used it has been invariably in the into solution. Next, 510 lbs. of oleum of about form of a viscous liquid in solution in nitrated 105% HzSOrStIGHiZthiS added slowly with con- :glycerine. The patent literature also discloses tinued cooling and stirring. When all of this that 20-25% solutions of nitrated sugar in nioleum has been added, the nitrated sugar will trated glycerine are preferred for reasons of have separated as a doughy plastic mass. This low viscosity and practicability of stabilization. s Separated from t acid a d t a f d to a 5 If stronger solutions of nitrated cane sugar in kneading tank supplied with a current of tap nitrated glycerine are made, it will be found very Water, where, in a short time the doughy mass difficult to stabilize the mixtures due to the viscosis converted to a fine, pulverulent precipitate ity of these higher sugar nitrate content solutions. which is filtered, washed With tap water and 40 If such sugars as cane sugar or glucose are nitransferred to a stirring tank containing dilute 4O trated alone, the product is always a gummy, alkali solution in which it is stirred for one hour taify-like substance which cannot be stabilized or more to stabilize the nitrated produ Which at ordinary temperatures except through costly consists of a mutual solid solution of nitrated and tedious re-solutions-and re-precipitations sugar and nitrated starch. The alkaline mixcombined with alkaline treatments, resulting in ture is th n filtered, W h W h p Wa er 45 Very poor yields, and dried at about 40 C.

'It is also known that if these gummy nitrated This dried l ed product is a slightly sugars are cooled to about 0 C. or lower, they y 1 W,. dusty, l w en i y p wd r, readily detbecome brittle and can be pulverized under ice onatable and soluble in the usual solvents used water and when in this finely divided condition, for gelatin explosives and for lacquers. When 50 can be treated with ice cold alkaline solutions made in the manner just described the product and thus stabilized. will contain about 14.50% N present as nitrate,

Applicant has discovered that under certain and its packing density will be about one-third conditions nitrated starch is very soluble in nithat of ordinary nitrostarch.

trated sugars and that the melting point of these Although I prefer the above described pro- 55 2 cedure for co-nitration. I do not confine myself to these narrow limits. It will readily be understood that one may vary the strengths of the acids used or their proportions or the proportions of sugar to starch, or the proportions of carbohydrate to acid, etc. and not depart from the spirit of this invention. Temperatures up to 30 C. may be used, for example, although I find that temperatures not in excess of C. are preferable. Instead of washing with Water, I may employ any aqueous solution of a neutral salt, or even a very dilute alkaline solution.

As an example of how I may nitrate with a mixed acid direct, instead of starting out with strong HNO3 and then adding the oleum later, I submit the following:

100 lbs. of finely ground cane sugar is thoroughly mixed with lbs. of dried starch and the mixture added to 1080 lbs. of a mixed acid consistingof:

Per cent H2804 64 HNOs 34 E20 2 The temperature of the nitration is preferably kept below 20 C. and the gummy nitration layer is removed and handled in the same manner as described in the example mentioned above, resulting in a fine, dry powder.

The product that I obtain by the practice of my present invention is quite different from any of the products which have been obtained by earlier workers in this field. The products obtained by the practice of my invention are pulverulent masses of a very light, fluffy nature, and appear to consist of what is known as a solid solution of nitrated starch and nitrated sugar, the two component materials not being present individually, but being combined or mutually dissolved. The nitrated product, unless compressed, is of very low apparent density, and is normally of a finely divided or pulverulent nature, even when not subjected to any comminuting operation.

I am aware that earlier Workers have nitrated colloided cellulose or parchmentized cellulose with sugar to obtain grains or masses of pulp, but my invention is quite distinct from this, as I do not employ cellulose in the practice of my invention, and I do not parchmentize or otherwise colloid the starch which I use, and the product which I obtain is not a granular nor a coherent mass, but is a very light, fiufiy pulverulent product consisting of nitrated starch and nitrated sugar in combination and apparently in mutually dissolved condition, in a form sometimes known as a solid solution.

By the practice of my present invention I obtain an explosive product in a very advantageous physical condition for use in the preparation of explosives mixtures. The finely divided condition, and the very low apparent density of my product, make it a particularly valuable component for use in explosive compositions where a low density or a high stick count is desired. Although I have described the use of sugars with starch in the preferred practice of my invention, I have discovered that the glycosides are the full equivalent of sugar in the practice of my invention, and when the glycosides of sugars are used in the practice of my invention they give products very similar in all respects to those obtained from the use of the particular sugar of which the glycoside is the derivative.

My invention relates to both the composition of matter and the process of making same as herein described. It will be evident that many modifications may be made within the limits of the disclosure as herein made, and accordingly no limitations should be placed upon my invention, except as indicated in the appended claims.

I claim:

1. As a new composition of matter a light, fluffy, pulverulent nitrated material consisting of a solid solution of nitrostarch in a predominating amount of nitrated sucrose, and containing not less than 8.4% of nitrostarch.

2. As a new composition of matter a light, fiuffy, pulverulent nitrated material consisting of a predominating amount of nitrated sucrose and of nitrostarch, said material containing not less than 8.4%, by weight, of nitrated starch, and being substantially free from individual particles of either pure nitrostarch or pure nitrated sucrose.

3. As a new composition of matter a stable, light, fiuffy pulverulent nitrated material consisting chemically of a predominating amount of nitrated sucrose and of nitrated starch, and containing not less than 8.4% of nitrated starch, but being substantially free from individual particles of either pure nitrostarch or pure nitrated sucrose.

4. The process which comprises forming a plastic mixture consisting of nitrated starch and a predominating amount of nitrated sucrose, such mixture containing not less than 8.4% of nitrostarch, in the presence of a fluid comprising nitric acid, at a temperature within the range of l0 C. and C., and thereafter transforming this plastic mass into a light, fluffy, pulverulent product by contact with water.

5. The process which comprises forming a plastic mixture consisting of nitrated-starch and a predominating amount of nitrated sucrose, such mixture containing not less than 8.4% of nitrostarch, in the presence of nitrating acid at a temperature within the range of -10 C. and 30 C., and thereafter transforming this plastic mass into a light, fiuify, pulverulent product by contact with a solution comprising water.

6. The process which comprises forming a plastic mixture consisting of nitrated starch and a predominating amount of nitrated sucrose, such mixture containing not less than 8.4% of nitrostarch, in the presence of nitrating acid at a temperature within the range of 10 C. and 30 C., and thereafter transforming this plastic mass into a light, flufiy, pulverulent product by contact with a dilute alkali solution.

JOSEPH A. WYLER. 

